Carboxylic acid amide mono azo-dyestuffs



United States Patent O ice 3,290,283 CARBOXYLIC ACID AMIDE MONOAZO-DYESTUFFS Karl Ronco, Muttenz, Switzerland, assignor to CibaLimited, Basel, Switzerland, :1 company of Switzerland No Drawing. FiledAug, 12, 1963, Ser. No. 301,642

Claims priority, application Switzerland, Aug. 17, 1962, 9,849/62; June28, 1963, 8,078/63 4 Claims. (Cl. 260-204) The present inventionprovides valuable new carboxylic acid amide azo dyestuffs free fromgroups imparting solubility in water, particularly sulfonic acid andcarboxylic acid groups, that correspond to the general formula in whichR and R represent benzene radicals, R represents a naphthalene radicalin which the azo, hydroxyl and carboxylic acid amide group are in 1-, 2-and 3- position respectively, R and R represent aryl radicals and thesymbols X represent carboxylic acid amide radicals. Of special interestare dyestuffs of the formula in which X represents a halogen atom or anitro, trifluoromethyl, carbalkoxy or cyano group, Y represents ahydrogen or a halogen atom or a trifiuoromethyl or alkyl group, Zrepresents a hydrogen or a halogen atom or an alkyl group, Z representsa hydrogen or a halogen atom and the symbols R represent benzeneradicals.

The new dyestuffsare obtained by condensing a monocarboxylic acid halidefree from acidic groups imparting solubility in water and correspondingto the formula (3) N=NRl H Rf OOHal with an amine of the formula HaN-RX-R;J

in a molar ratio of 1:1 in which formulae the radicals R to R and X havethe meanings given above.

The azo carboxylic acids corresponding to Formula 3 are obtained bycoupling a diazo compound of an aromatic monamine free from acidicgroups imparting solubility in water, especially an aminobenzene, with a2-hydroxy-3-naphthoic acid. As diazo bases the following amines may bementioned:

4-amino-3-nitrotrifluoromethylbenzene,5-amino-2-nitrotrifluoromethylbenzene,3-amino-4-nitrotrifluoromethylbenzene, 4-chloro-2-nitro-l-aminobenzene,3-aminotrifluoromethylbenzene, 5-chloro-2-aminobenzoic acid methylester, Anthranilic acid methyl ester,

2 4: 5 -trichloro-1 -aminobenzene,

2 S -dichloro-1-aminobenzene,

2 :4: 6-trichlorol-arninobenzene,

3,290,283 Patented Dec. 6, 1966 4-methyl-2-nitro-1-aminobenzene,2-methyl-5-nitro-l-aminobenzene, 2-nitro-1-aminobenzene,S-nitro-I-aminobenzene, 2:4-dinitro-l-aminobenzene,S-methyl-Z-methoxy-l-arninobenzene,

2 S-difluoro- 1 -aminobenzene,

3 S-di- (trifluoromethyl -1-aminobenzene, 4chloro-3-amino-trifluoromethylbenzene, 2-methyl-5-chloro-l-aminobezene,Z-methoxy-S-nitro-l-aminobenzene, 2-nitro-4-methoxy-l-aminobenzene,Z-methoxy-S-chloro-l-aminobenzene, 4-nitro-2-cyano-l-aminobenzene, and

2 5-dimethyl-4-chloro-l-aminobenzene.

The azodicarboxylic acids so obtained are treated with agents capable ofconverting carboxylic acids into their acid halides, for example, theiracid chlorides or bromides, particularly phosphorus halides such asphosphorus pentabromide, phosphorus trichloride or phosphoruspen'tachloride, phosphorus oxy halides and advantageously thionylchloride.

The treatment with such acid halogenating agents is advantageouslycarried out in an inert organic solvent, for example,dirnethylformamide, chlorobenzenes, for example, monoordi-chlorobenzene, toluene, xylene or nitrobenzene; the last fivesolvents may be used together with dimethylformamide if desired.

In the preparation of the carboxylic acid halides it is generally ofadvantage first to dry the azo compounds which have been prepared in anaqueous medium, or to free them from water by azeotropic distillation inan organic solvent. If desired, this azeotropic drying process can becarried out immediately prior to the treatment with the acidhalogenating agents.

The azo dyestuff carboxylic acid halides so obtained are condensed in amolar ratio of 1:1 with an amine of the Formula 4, especially with anaminobenzene dicarboxylic acid dianilide of the formula (5) C O NHR HzNCONHR in which the symbols R represent benzene radicals. Of specialinterest are the aminoterephthalic acid dianilides of the formula (6)CONHR;

CONHR4 in which the symbols R represent benzene radicals.

As examples of aminobenzene dicarboxylic acid diarylides the followingmay be mentioned: aminoterephthalic acid dianilide, aminoterephthalicacid-di-(para-chloranilide), aminoterephthalic acid-bis- 2 5-dichloranilide aminoterephthalic acid-di-(meta trifluoromethylanilide),aminoterephthalic acid-di-(a-naphthylamide)1-amin0-3:S-benzenedicarboxylic acid dianilide,

1 amino-3:S-benezenedicarboxylic acid-di-(para chloranilide), andaminoterephthalic acid-di-(para-methoxyanilide).

Instead of aminobenzene dicarboxylic acid diarylides,diaroyltriaminobenzenes can also be used as amines of Formula 4,especially those of the formula IIIHCORA NHGOR4 in which the symbols Rrepresent benzene radicals, for example1-arnino-2:S-dibenzoylaminobenzene and 1- amino-2 -di-(para-chlorobenzoylamino -benzene.

As further monamines there may be mentioned those of the formula C ONHRsin which R; and R represent benzene radicals.

The condensation of the carboxylic acid halides of the type definedabove with the amines is advantageously carried out in an non-aqueousmedium. Under these conditions the reaction generally proceedssurprisingly easily at temperatures Within the boiling range of thecommon organic solvents, for example, toluene, monochlorobenzene,dichlorobenzene, trichlorobenzene, nitrobenzene, and the like. In orderto accelerate the reaction it is generally of advantage to use an agentcapable of binding acid, for example, anhydrous sodium acetate orpyridine. Some of the dyestuifs so obtained are crystalline and othersare amorphous. They are generally obtained in a very good yield and in apure state. It is of advantage first to separate the acid chloride fromthe carboxylic acid. In some cases, however, the isolation of the acidchloride may be dispensed with without harm, and condensation carriedout immediately following the preparation of the carboxylic acidchloride.

The new dyestuffs are valuable pigments and can be used for a Widevariety of purposes. For example, they can be used in a finely dividedform for the spin-dyeing of rayon and viscose or cellulose ethers andesters or polyamides or polyurethanes, and also for the manufacture ofcolored lacquers or lakes. They are also suitable for coloring solutionsor products of cellulose acetate, nitrocellulose, natural or syntheticresins such as polymerization or condensation resins, for example,arninoplasts, alkyd resins, phenoplasts, polyolefines such aspolystyrene, polyvinyl-chloride, polyethylene, polypropylene, andpolyacrylonitrile, rubber, casein, silicone and silicone resins. Theycan also be used in the manufacture of colored pencils, cosmeticpreparations or laminated sheet material. The new dyestulfs aredistinguished by a very good fastness to light and to migration. Eventhose dyestuffs of the invention that do not possess a halogen in thearylide radical yield dyeings exhibiting an excellent fastness to light.It may also be mentioned that, by a suitable choice of components,yellow tints can be obtained with the dyestulfs of the invention, whichis otherwise not possible with fi-hydroxynaphthoic acid arylide azodyestuffs.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

Example 1 61 parts of the dyestuff, obtained by diazotising4-trifluoromethyl-Z-nitro-l-aminobenzene in glacial acetic acid or withnitrosyl sulfuric acid and coupling with 2:3- hydroxy-naphthoic acid,were heated for 1 hour at 120 to 125 C., while stirring, with 600 partsof ortho-dichlorobenzen, 2.5 parts of dimethylformamide and 25 parts ofthionyl chloride. After cooling the reaction mixture, the precipitatedhomogeneous crystalline monocarboxylic acid chloride of the dyestufi wasisolated by filtration, washed with a small amount of coldortho-dichlorobenzene and benzene, and dried in vacuo at to C.

8.5 parts of the chloride so obtained were stirred into 500 parts ofcold ortho-dichlorobenzene. A warm solution of 7 parts ofZ-aminoterephthalic acid diphenylamide in 500 parts ofortho-dichlorobenzene was then added and the mixture stirred for 15hours at 140 to 145 C. The pigment, which consisted of small, uniformlybent needles, was then filtered off at 100 to 110 C., washed with hotortho-dichlorobenzene, hot benzene, methanol and water, and thendried invacuo at to C. The condensation dyestuif of the formula 0 ONE- formed ayellow-orange pigment which was sparingly soluble to insoluble in theusual solvents and colored polyvinylchloride foil reddish yellow tintspossessing an excellent fastness to light and migration.

I II III IV 1 4-trifluoromethyl-Z-nitro-l-amino- 2:3-hydr0xynaphthoicacid Z-aminoterephthalic acid bis-(2 :5- Reddish yellow.

benzene. dichlorophenylamide) 2 do do 2-amin0terephthalc acidbis-(4-ch1o- Do.

rophenylamide) 3 do l:4-di-(4-chlorobenz0ylamino)-2- Orange.

aminobenzene. 4 "do do S-amino-isophthalic acid diphenyl- D0.

amide. 5 do d0 5-amino-is0phthalic acid bis-(4- Do.

chlorophenylamide). 6 d0 2-aminotercphthalic acid bis-(3-tri-Yellow-Orange.

fluoromethylphenylamide) 7 d0 do Z-aminoterephthalic acid di-a-naph- Do.

thylamide. 8 5-trifiuoromethy1-2-nitro-l-aminod0 2-aminoterephtha1icacid diphenyl- Orange.

benzene. amide. 9 4-chloro-2-nitro-l-aminobenzene do .xln Do.

do 5-amino-isophthalic acid bis-(4- Red-orange.

chlorophenylarnide). 11 3:5-d1(trifluorornethyD-l-ammod0 1:4-di-(4-chlorobenzoylamino)-2- Orange.

benzene. aminobenzene. 12 2:4:5-trichloro-1-ammobeuzene d0Z-amiraoterephthalic acid diphenyl- Red-orange.

ami e. 13 5-chloro-2aminobenzoic acid methyl 2:3-hydroxynaphthoic acidE-aminoisophthalic acid diphenyl- Orange.

es er. am e. 14 4-trifluoromethyl-2-nitro-l-amino-6-br0mc-2:3-hydroxy-naphth0ic acid- 2-aminotcrephtha1ic acid diphenyl-Do.

benzene. amide. 15 s-ttigifluoromethyl-Z-chloro-l-amino-2:3-hydr0xynaphth0ic acid do Do.

enzene. 16 2:5-di1nethyl-4chloro-l-aminobenzened01:4-di-(4-chlorobenzoylamino)-2- Red.

aminobenzcne). 17 2:4-di11itr0-1-aminobenzene. .d0 0 Redprange 184-nitro-2-cyano-l-a1ninobmvene .do Z-amiraoterephthalic acid diphenyl-Scarlet.

arm e.

65 parts of stabilized polyvinyhchloride, 35 parts of dioctyl phthalateand 0.2 part of the dyestuff obtained in the manner described in thesecond paragraph of Example 1 were mixed together, and the mixtureworked to and fro for 7 minutes at 140 C. on a two-roll calender. Areddish yellow foil possessing a very good fastness to light and tomigration was obtained.

Example 3 0.25 part of the dyestuff obtained in the manner described inExample 1, 40 parts of an alkyd-melamine stoving enamel containing 50%of solid substance, and 4.175 parts of titanium dioxide were ground for24 hours in a rod mill. A thin coating of the enamel so obtained wasspread on to aluminum foil and stoved for 1 hour at 120 C.

The reddish yellow enamel coating so obtained exhibited a good fastnessto light.

Example 4 i 40 parts of a nitrocellulose lacquer, 2.375 parts oftitanium dioxide and 0.125 part of the dyestnif obtained in the mannerdescribed in Example 1 were ground for 1.6 hours in a rod mill. A thincoating of the lacquer so obtained was spread on to aluminum foil. Thereddish yellow lacquer coating so obtained possessed very goodproperties of fastness.

What is claimed is:

1. An azo-dyestutf of the formula X1 -on o ONHR4 Z: -0 ONE- o ONHR4 6 inwhich R represents a benzene radical, X is a member selected from thegroup consisting of chlorine, nitro and trifluloromet-hyl, Y istrifluorornethyl, and Z is a member selected from the group consistingof hydrogen and bromine.

2. An azo-dyestult of the formula N=N- OF OH N02 CONHRA -GONH CONHR inwhich R represents a benzene radical.

3. The dyestutf of the formula ONH 4. The dyestufi of the formula (ill CONH l I 0 F OONH References Cited by the Examiner UNITED STATES PATENTS1,947,550 2/ 1-934 Hitch 260-204 XR 2,210,072 8/ 1940 Fischer 260-204 XR3,086,006 4/ 1963 Lohe et al. 260-204 CHARLES B. PARKER, PrimaryExaminer.

R. I. FINN-EGAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIGN Patent No.3,290,283 December 6, 1966 Karl Ronco ertified that error appears in theabove numbered pat- It is hereby c ction and that the said LettersPatent should read as ent requiring corre corrected below.

Column 5, line 42, the formula should appear as shown below instead ofas in the patent:

J N'-.. -=N

-- OH CONHR Z CONH CONHR Signed and sealed this 7th day of November1967.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J BRENNER Attesting Officer Commissioner ofPatents

1. AN AZO-DYESTIFF OF THE FORMULA